Zhou Shiqi
School of Physics Science and Technology, Central South University, Changsha, Hunan, China.
J Chem Phys. 2008 Mar 14;128(10):104511. doi: 10.1063/1.2888977.
Phase diagram is calculated by a recently proposed third-order thermodynamic perturbation theory (TPT) for fluid phase and a recently proposed first-order TPT for solid phases; the underlying interparticle potential consists of a hard sphere repulsion and a perturbation tail of an attractive inverse power law type or Yukawa type whose range varies with bulk densities. It is found that besides usual phase transitions associated with density-independent potentials, the density dependence of the perturbation tail evokes some additional novel phase transitions including isostructural solid-solid transition and liquid-liquid transition. Novel triple points are also exhibited which includes stable fluid (vapor or liquid)-face-centered cubic(fcc)-fcc and liquid-liquid-fcc, metastable liquid-body-centered cubic(bcc)-bcc. It also is found that the phase diagram sensitively depends on the density dependence and the concrete mathematical form of the underlying potentials. Some of the disclosed novel transitions has been observed experimentally in complex fluids and molecular liquids, while others still remain to be experimentally verified.
相图是通过最近提出的用于流体相的三阶热力学微扰理论（TPT）和最近提出的用于固相的一阶TPT计算得到的；粒子间的基础势由硬球排斥力和吸引性逆幂律型或 Yukawa 型的微扰尾组成，其范围随体密度而变化。研究发现，除了与密度无关的势相关的常见相变外，微扰尾的密度依赖性还引发了一些额外的新型相变，包括同结构的固 - 固转变和液 - 液转变。还展示了新型三相点，包括稳定的流体（蒸汽或液体） - 面心立方（fcc） - fcc 和液 - 液 - fcc，亚稳的液体 - 体心立方（bcc） - bcc。还发现相图敏感地依赖于基础势的密度依赖性和具体数学形式。一些所揭示的新型转变已在复杂流体和分子液体中通过实验观察到，而其他一些仍有待实验验证。
